New carbazole derivatives of the dianthraquinonylamine-acridone series



iri:

Patented Dec. 22, 1931 D? PATENEQQFFICE I ROBERT IBERLINER, E LEvEExusEE-oN-rHE-EHI E, eERfiANx, A ssIeNon T0 GEN- ERAL amnrnnvvonxs, me, or NEW YORK,1\T. Y., A CORPORATION or DELAWARE NEW oAEBAzoEE DERIVATIVES OF THE DmNrHRAQuINoNrimMrnE hoEIDONE SERIES 1 N0 Drawing. a licat on filed July so, 1929, Serial No. 382,279, and in eer afi au ust 7, 1928.

The present invention relates to a process of preparing carbazole derivatives of the diwherein the nuclei marked I and II may be substituted by halogenatonis, are obtainable by reacting upon the corresponding dianthra-' quinonylamine-acridonecompounds about -40 O. untilno more change in color occurs, and oxidizing the'intermediate prod not thus formed eitherby, prolonged heating of the sulfuric acid solution, lor by means of an oxidizing agent such assodium nitrite.

The working; up of thereaction mixture may be performedfin the usual manner, for instance by pouring the melt into ice water, filtering and Washing.

Oxidation may also be performed by adding the oxidizing agent, such as an alkali metal nitrite, chromic acid,1or the like to ice Water and then pouring the unoxidiz ed sulfuric acidsolutioninto "the vvater,

a greenish blue coloration, they are difficultly soluble in the usual organic solvents dye '(obtainable, for instance,lby chlorination of 'anthraquinone N 1 2acrido'ne ,in- 'nitrobenyv'eight of 'cupric chloridiin eoo arts by 'vveight of naphthalene; [The condensation product, which separates' in wellgformed,

. customary manner. with strong sulfuric acid1at a-temperature between V cotton from a yellovir-oli ve liydrosulphite vat clear and fast green'sha'des! The invention may befgillustrated by the following eXamPIeabut is not restricted thereto; e l fiiww 1 u c y 21 parts by weightlof trichloroanthraquinone acridone of the probable formula for several hours 7 to boiling with. '10"parts Weight of sodium acetateand onepartby small, dark crystals, "i svvorked Pup i1 .ithe

5 (p rt y We gh o he-d h h 'q n acridonylaminej are dissolved at about C. in parts ,b'y weight of concentrated sulfuric acid. which is at first yellovvish-brown, changes; already after ashort time to olive. When no further chahgegoccurs in the coloration of the solution, the melt-is poured into 500 parts of Water, to Which 3 parts by Weight of sodium nitrite have been/added and heating is effected for ihalf an hour at (1' The coloration of the solution,

The new dyestulf isflthus obtained in the form;

of green flakes, which are 9 filtered and washed. Instead ,ofusing'the sodium nitrite dissolved in Water, the calculated quantity of sodium nitrite can also be added to the sulfuric acid solution, whereupon the original olive colorationpfithe solution changes to a clear greenish-blue. The dyestufi' dyes cotton from a yellowish-olive vat fast green 1,

not of 11 mol' of itricliloroanthraquimne acrii The oxidation. can; also be earried outwith for instance,'chro-1rrifc acid.

When startinginstead of trichloroanthraquinone acridone. with the corresponding trib-romoanthraquinpneacridone and further working as described and vthis example a 7 Very} similar properties is ob- 30 compound of mined. x I i Emmpk2 @partsrby weight of .thelcondensation proddonelwi'th "limol of ,tamino-anthraqui'rione ac-ri done are dissolved at.about2(l3(1 G1 ,50 parts by weight of concentratedsulfurie acid and the reaction mixture is further itizeatedas described Example 1- A dyestu-fi isthus obtainedpossessing similar propertiesrtothat of ExampIe'Lbut dyeing 0011- ton a: slightly more yel'lowishrgreenshade.

I claim:-

1w The process which comprises reacting uponf'a compound ofv the general formula:

other customary oxidizing agents, such as,-

'wherein the nuclei 1 and 1 may be wherein the nuclei I and'IIVmay be substituted by halogen atoms, with strong sulfuric acid at a temperature between'about 1040 C. and oxidizing the intermediate product thusformedr j o V 2 The proeesswhich, comprises Ereacting upon a compound of the general formula o st 1 V wherein the ws stand for halogen atoms, with strong sulfuric acid at atemperature between about 1040 C. and oxidizing the intermediate roducts thus obtained.-

3. s new products, the compounds of the ..1i00

probable general-iormula c stituted by halogen atoms; said products being green powders soluble in concentrated sulfuric: acid with blueish-green colorations, dyeing cotton from' an alkaline" hydrosulfite vat clear and fast green shades.

4:. As new products, the compounds of the probable general formula wherein the ws stand for halogen atoms,

said products being green powders, soluble in concentrated sulfuric acid with a greenishblue coloration, dyeing cotton from an alkaline hydrosulfite Vat, clear and fast green shades.

5. As a new product, the compound of the I probable formula:

said compound formin a green powder, soluble in concentrated sul ric acid with a greenish-blue coloration, dyeing cotton from a yellowish-olive Vat fast green shades.

In testimony whereof, I aflix my signature. 7

ROBERT BERLINER. [1,. s.] 

